US8454818B2 - Method for operating copper electrolysis cells - Google Patents

Method for operating copper electrolysis cells Download PDF

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Publication number
US8454818B2
US8454818B2 US12/675,601 US67560108A US8454818B2 US 8454818 B2 US8454818 B2 US 8454818B2 US 67560108 A US67560108 A US 67560108A US 8454818 B2 US8454818 B2 US 8454818B2
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electrolyte
inflow
copper electrolysis
outflow
cell
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US20110056842A1 (en
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Andreas Filzwieser
Iris Filzwieser
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Mettop GmbH
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Mettop GmbH
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells

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  • the invention relates to a process for the operation of copper electrolysis cells comprising a plurality of anode and cathode plates arranged vertically and parallel to each other, a longitudinal electrolyte inflow and an electrolyte outflow, as well as to a new copper electrolysis cell.
  • copper in the form of copper(II)ions is solubilized anodically in a copper electrolysis and precipitates on the cathode to form again metallic copper.
  • m is the mass of copper produced in g
  • M is the molar mass of copper in g/mol
  • i is the current density in A/m 2
  • A is the electrode surface in m 2
  • t is the time in s
  • z is the valency of the ions involved in the reaction
  • F is the Faraday constant in As/mol. If it is desired to increase the amount of copper produced with a given plant size (A), only the current density i can be increased.
  • This theoretical limiting current density i Limit (Equation 2) is a function of the copper ion concentration in the electrolyte (c 0 ) and the diffusion layer thickness ⁇ N at the electrode. N, the number of ions involved in the process, F, the Faraday constant and D, the diffusion coefficient, are constant.
  • the configurations of refining electrolysis cells which are used today are characterized in that the electrolyte is supplied on the front side and discharged on the opposite front side.
  • the main flow thus occurs between the cell wall and the electrodes or the cell bottom and the lower edges of the electrodes, respectively.
  • This flow applied from the outside also referred to as a forced convection
  • the flow between the electrodes is determined by the natural convection resulting from the density differential of the electrolyte in front of the cathodes (lighter electrolyte due to the depletion of copper ions) and in front of the anodes (heavier electrolyte due to the accumulation of copper ions), respectively.
  • So-called channel cells have been developed in which a parallel flow is applied at a relatively high speed, wherein screen-shaped flow-rate fixtures are necessary in the electrolyte inflow part in front of the electrode groups in order to ensure a uniform flow distribution across the entire channel cross-section.
  • Parallel flow cells with double-walled partition walls are likewise known, wherein one wall is flush with the upper bath edge, but does not reach the bath bottom, whereas the other wall starts at the bath bottom, but does not reach the upper edge.
  • double- or also multiple-walled partition walls with openings distributed across the entire width are arranged, which are located, on one side, at the height of the lower cathode edge and/or slightly upwards and, on the other side, at the height of the electrolyte level and/or slightly downwards.
  • containers for electrolytic metal production are known in which, in order to achieve a parallel flow, the electrolyte inflow and outflow into and from the electrode space, respectively, occur through perforated plates arranged parallel to the longitudinal walls.
  • a parallel partition wall with openings for the electrolyte passage into the electrode space is arranged on only one longitudinal wall.
  • the through openings are distributed across the entire electrode height and are oriented toward the electrode gaps.
  • a comparatively simple measure for achieving a parallel flow in conventional electrolysis cells consists in the arrangement of tubular electrolyte inflow and outflow devices through which the electrolyte in the two free spaces between the longitudinal bath walls and the lateral electrode edges is guided in opposite directions. Due to the larger cathode width, a congestion of the electrolyte occurs in front of the lateral cathode edges, whereby said electrolyte flows partly into the respective electrode gap.
  • An electrolyte bath is also known in which the parallel flow is achieved via an inflow of the electrolyte from the bath bottom.
  • the electrolyte inflow openings are located beneath the anodes and are oriented vertically upwards.
  • an electrolysis cell having a longitudinal electrolyte inflow wherein an electrolyte inflow box running across the entire bath length, extending as far as slightly underneath the lower cathode edge, closed at the bottom and on the sides, open above the electrolyte level is mounted to one or both longitudinal sides, which electrolyte inflow box comprises through openings on the side facing the electrodes, which through openings are oriented horizontally and parallel to the electrodes and extend across a certain area of the cathode gaps in the area of the lower cathode edges.
  • the cross-sectional area of all through openings is smaller than the open horizontal cross-sectional area on the top side of the electrolyte inflow box in order to achieve a slight overpressure.
  • the channel cell requires a high pumping capacity in order to achieve high flow velocities.
  • continuous electrolyte filtration is required for separating the entrained anode sludge.
  • electrolyte inflow openings in the bath bottom are unsuitable because of the risk of anode sludge being whirled up.
  • the flow conditions are unsatisfactory for the same reasons. Due to the independent partition wall which has a relatively strong design, the bath width increases substantially, which involves a larger space requirement.
  • the present invention aims to avoid the above-mentioned disadvantages and problems of the prior art and has as its object to provide a process for operating (conventional) copper electrolysis cells as well as a copper electrolysis cell, by means of which higher current densities and hence higher current yields than in the prior art are possible, but the cathode quality is not impaired, e.g., by the anode sludge being whirled up, a disturbance in the anode sludge precipitation or a poor inhibitor distribution. Similarly, extensive changes to the cell and expensive installations in the cell are to be avoided.
  • said object is achieved in a process of the initially mentioned kind in that the electrolyte is injected via the electrolyte inflow horizontally and parallel to the electrodes in each electrode gap always at the height of the lower third of the electrodes at a speed of from 0.3 to 1.0 m/s, with the cathode plates being arranged stationarily relative to the inflow direction.
  • an optimization of the flow guidance in the electrolysis cell based on a maximum relative motion from the electrolyte to the electrode is achieved, which advantageously results in a reduction of the hydrodynamic boundary layer, an equalization of the concentration and temperature of the electrolyte, a better distribution of the inhibitors and, above all, an increase in the limiting current density.
  • FIGS. 1 a - 1 c are graphs illustrating velocity distribution of electrolyte flow between electrodes.
  • FIG. 2 is a schematic illustration of a copper electrolysis cell.
  • FIGS. 3 and 4 illustrate an embodiment of an arrangement of nozzles and cathode plates of an electrolysis cell.
  • the electrolyte is injected into the cell at a speed of from 0.3 to 0.6 m/s.
  • a further improvement of the process is possible if the electrolyte is not allowed to flow out on the front side of the cell, as it is common and used in the examples, but on the longitudinal side.
  • the process according to the invention has the additional advantage that it can be performed also in already existing electrolysis cells without major effort and with few changes to the existing equipment.
  • a copper electrolysis cell comprising a plurality of anode and cathode plates arranged vertically and parallel to each other, a longitudinal electrolyte inflow and an electrolyte outflow
  • the electrolyte inflow comprises a closed inflow box extending along a longitudinal wall of the cell as far as into the area of the lower electrode edge, which inflow box can be hooked in on the front sides of the cell and is connectable to an electrolyte source and is provided with means for the stationary arrangement of each cathode plate as well as, in the areas extending across the lower third of the electrode height and, in each case, corresponding to the electrode gap, with at least one opening, in particular nozzle, for a directed electrolyte supply.
  • the means for the stationary arrangement of the cathode plates are designed as means for vertical guidance.
  • the means for vertical guidance are designed as circular disks or wheels, with the cathode plates, in each case, being centered between two disks or wheels, respectively, arranged adjacent to each other and spaced apart from each other.
  • the electrolyte outflow is arranged on the front side.
  • it may also be arranged on the longitudinal side.
  • the electrolyte inflow box used in the cell according to the invention is usable advantageously also in already existing conventional electrolysis cells.
  • FIG. 2 shows a schematic illustration of a copper electrolysis cell according to the present invention, in which, for the sake of better distinguishability, the electrolyte inflow box according to the invention has been emphasized graphically in relation to the electrolysis cell itself.
  • the closed inflow box 1 extends along a side wall 3 of the bath 2 and is fixably hooked into the cell at the front walls 4 of the bath 2 , with the hooking devices 5 serving simultaneously for the supply and removal of the electrolyte into and from the actual inflow box.
  • the inflow box 1 is connectable to an electrolyte source, e.g., via a flange joint 6 .
  • the inflow box 1 is arranged so deep in the cell that it extends as far as into the area of the lower electrode edge.
  • openings, in particular nozzles 7 facing the electrodes are arranged, with at least one opening being located in each area corresponding to the electrode gap and extending across the lower third of the electrode height ( FIG. 3 ).
  • the electrolyte is injected into the cell in the lower area of the electrode gap at a speed of from 0.3 to 1.0 m/s in order to obtain the advantageous flow guidance mentioned further above.
  • the stationary arrangement is achieved by means for the vertical guidance of the cathode plates which are designed as circular disks or wheels 8 , with the cathode plates 9 , in each case, being centered between two disks or wheels, respectively, arranged adjacent to each other and spaced apart from each other ( FIG. 4 ).
  • the cathode plates which are designed as circular disks or wheels 8
  • the cathode plates 9 in each case, being centered between two disks or wheels, respectively, arranged adjacent to each other and spaced apart from each other. 4 .
  • a conventional industrial copper electrolysis cell has been equipped with an electrolyte inflow according to the invention comprising an inflow box as described above.
  • Copper sheets were produced in an industrial electrolysis cell with an inflow speed of 0.75 m/s and a current density of 407 A/m 2 . During the entire anode period, the cathodic current yield was more than 97%.
  • Copper sheets were produced in an industrial electrolysis cell with an inflow speed of 1.0 m/s and a current density of 498 A/m 2 . During the entire anode period, the cathodic current yield was more than 93%.
  • Copper sheets were produced in an industrial electrolysis cell with an inflow speed of 0.5 m/s and a current density of 498 A/m 2 . During the entire anode period, the cathodic current yield was more than 98%.
  • Copper sheets were produced in an industrial electrolysis cell with an inflow speed of 0.67 m/s and a current density of 543 A/m 2 . During the entire anode period, the cathodic current yield was more than 95%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
US12/675,601 2007-08-27 2008-08-07 Method for operating copper electrolysis cells Active 2030-02-01 US8454818B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ATA1337/2007 2007-08-27
AT0133707A AT505700B1 (de) 2007-08-27 2007-08-27 Verfahren zum betreiben von kupfer-elektrolysezellen
PCT/AT2008/000277 WO2009026598A2 (de) 2007-08-27 2008-08-07 Verfahren zum betreiben von kupfer-elektrolysezellen

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US20110056842A1 US20110056842A1 (en) 2011-03-10
US8454818B2 true US8454818B2 (en) 2013-06-04

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US12/675,601 Active 2030-02-01 US8454818B2 (en) 2007-08-27 2008-08-07 Method for operating copper electrolysis cells

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US (1) US8454818B2 (de)
EP (1) EP2183409B1 (de)
JP (1) JP5227404B2 (de)
CN (1) CN101376990B (de)
AT (2) AT505700B1 (de)
AU (1) AU2008291662B2 (de)
CA (1) CA2696635C (de)
DE (1) DE502008003297D1 (de)
ES (1) ES2365376T3 (de)
PL (1) PL2183409T3 (de)
WO (1) WO2009026598A2 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201112606D0 (en) 2011-07-22 2011-09-07 Johnson Matthey Plc Desulphurisation materials
JP5632340B2 (ja) * 2011-08-05 2014-11-26 Jx日鉱日石金属株式会社 水酸化インジウム及び水酸化インジウムを含む化合物の電解製造装置及び製造方法
CN103255443B (zh) * 2013-05-06 2015-11-25 阳谷祥光铜业有限公司 超高电流密度电解或电积槽
CN104018191B (zh) * 2014-06-16 2017-01-11 南华大学 带流量控制管的电解槽
JP6410131B2 (ja) * 2014-07-31 2018-10-24 佐々木半田工業株式会社 錫の高電流密度電解精製法
CN104831319A (zh) * 2015-05-28 2015-08-12 杭州三耐环保科技股份有限公司 一种顶部进液双向平行流电解槽及其使用方法
CN105506670B (zh) * 2015-12-18 2018-03-23 阳谷祥光铜业有限公司 一种铜电解或铜电积的装置与运行方法
GB201603224D0 (en) 2016-02-24 2016-04-06 Barker Michael H And Grant Duncan A Equipment for a metal electrowinning or liberator process and way of operating the process
JP7150768B2 (ja) * 2020-01-30 2022-10-11 Ｊｘ金属株式会社 電解装置及び電解方法
JP7150769B2 (ja) * 2020-01-30 2022-10-11 Ｊｘ金属株式会社 電解装置及び電解方法

Citations (10)

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Publication number Priority date Publication date Assignee Title
US3558466A (en) * 1968-03-04 1971-01-26 Kennecott Copper Corp Electrolytic cell
BE771215A (en) 1970-06-24 1971-12-16 Mansfeld Kom Wilhelm Veb Copper electrorefining bath - comprising several units with hollow connecting walls
US3682809A (en) * 1970-02-24 1972-08-08 Kennecott Copper Corp Electrolytic cell constructed for high circulation and uniform flow of electrolyte
DD109031A1 (de) 1973-11-22 1974-10-12
US3966567A (en) * 1974-10-29 1976-06-29 Continental Oil Company Electrolysis process and apparatus
DD125714A1 (de) 1976-04-21 1977-05-11
EP0146732A1 (de) 1983-11-08 1985-07-03 Holzer, Walter, Senator h.c. Dr.h.c.Ing. Arbeitsverfahren und Vorrichtung zur Ausübung des Verfahrens zur Abscheidung von z.B. Kupfer aus flüssigen Elektrolyten, der durch einen mehrzelligen Elektrolysebehälter geführt wird
US5066379A (en) * 1990-06-14 1991-11-19 Corrosion Technology, Inc. Container for corrosive material
US5492608A (en) 1994-03-14 1996-02-20 The United States Of America As Represented By The Secretary Of The Interior Electrolyte circulation manifold for copper electrowinning cells which use the ferrous/ferric anode reaction
US5855756A (en) * 1995-11-28 1999-01-05 Bhp Copper Inc. Methods and apparatus for enhancing electrorefining intensity and efficiency

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Publication number Priority date Publication date Assignee Title
JPS4919003Y1 (de) * 1970-01-22 1974-05-21
JPS5237602Y2 (de) * 1972-05-29 1977-08-26
JPH0768629B2 (ja) * 1987-07-06 1995-07-26 三菱マテリアル株式会社 ユニット化された極板を用いた電解方法
JPH0389166U (de) * 1989-12-25 1991-09-11
JP2002105684A (ja) * 2000-09-29 2002-04-10 Dowa Mining Co Ltd 電解方法及びこれに使用する電解槽

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558466A (en) * 1968-03-04 1971-01-26 Kennecott Copper Corp Electrolytic cell
US3682809A (en) * 1970-02-24 1972-08-08 Kennecott Copper Corp Electrolytic cell constructed for high circulation and uniform flow of electrolyte
BE771215A (en) 1970-06-24 1971-12-16 Mansfeld Kom Wilhelm Veb Copper electrorefining bath - comprising several units with hollow connecting walls
DD109031A1 (de) 1973-11-22 1974-10-12
US3966567A (en) * 1974-10-29 1976-06-29 Continental Oil Company Electrolysis process and apparatus
DD125714A1 (de) 1976-04-21 1977-05-11
EP0146732A1 (de) 1983-11-08 1985-07-03 Holzer, Walter, Senator h.c. Dr.h.c.Ing. Arbeitsverfahren und Vorrichtung zur Ausübung des Verfahrens zur Abscheidung von z.B. Kupfer aus flüssigen Elektrolyten, der durch einen mehrzelligen Elektrolysebehälter geführt wird
US4581115A (en) 1983-11-08 1986-04-08 Walter Holzer Apparatus for the precipitation of copper from a liquid electrolyte conducted through a multi-cell electrolytic tank
US5066379A (en) * 1990-06-14 1991-11-19 Corrosion Technology, Inc. Container for corrosive material
US5492608A (en) 1994-03-14 1996-02-20 The United States Of America As Represented By The Secretary Of The Interior Electrolyte circulation manifold for copper electrowinning cells which use the ferrous/ferric anode reaction
US5855756A (en) * 1995-11-28 1999-01-05 Bhp Copper Inc. Methods and apparatus for enhancing electrorefining intensity and efficiency

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Krishnae et al Enhancement of operating current density in a copper electrowinning cell, Hydrometallurgy, vol. 31, 1992, pp. 243-255. *
Lapicque et al, Modelling of a continuous parallel plate plug flow electrochemical reactor: electrowinning of copper, Journal of Applied Electrochemistry, vol. 15, 1985, pp. 925-935. *

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Publication number Publication date
AT505700A1 (de) 2009-03-15
ES2365376T3 (es) 2011-10-03
DE502008003297D1 (de) 2011-06-01
WO2009026598A3 (de) 2009-08-13
CA2696635C (en) 2014-10-07
EP2183409A2 (de) 2010-05-12
CN101376990A (zh) 2009-03-04
AU2008291662A1 (en) 2009-03-05
ATE506467T1 (de) 2011-05-15
CA2696635A1 (en) 2009-03-05
CN101376990B (zh) 2012-09-05
JP2010537051A (ja) 2010-12-02
AT505700B1 (de) 2009-12-15
AU2008291662B2 (en) 2011-10-06
JP5227404B2 (ja) 2013-07-03
PL2183409T3 (pl) 2011-11-30
WO2009026598A2 (de) 2009-03-05
EP2183409B1 (de) 2011-04-20
US20110056842A1 (en) 2011-03-10

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